Metal-conjugated microporous polymers

ABSTRACT

A catalyst which can catalyze ring-addition reaction of CO 2  and an alkylene oxide at 0˜180° C. under 0.1˜8.0 MPa to produce a corresponding cyclic carbonate, and the preparation thereof. The catalyst is a conjugated microporous macromolecule polymer complexed with cobalt, chromium, zinc, copper or aluminium, and by using the macromolecule catalyst complexed with different metals to catalyze the reaction of CO 2  and alkylene oxide at normal temperature and normal pressure, a yield of the corresponding cyclic carbonate of 35%-90% can be obtained. The catalyst is easy to recover and the re-use of the catalyst has no influence on the yield; additionally, the yield can reach over 90% by controlling the reaction conditions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.14/114,663 which is a U.S. national stage application of internationalpatent application No. PCT/CN2012/082948, filed on Oct. 15, 2012, whichclaimed priority from China Patent Application Nos. 20110427079.2 filedon Dec. 19, 2011, 201210135309.2 filed on on May 3, 2012, and20120272056.3 filed on Aug. 1, 2012, the content of which areincorporated here by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

In this invention, a series of new metals including Co, Cr, Zn, Cu, andAl coordinated conjugated microporous polymer catalysts were designed,synthesized, and used to catalyze the reaction of the epoxides and CO₂to produce corresponding cyclic carbonates at mild conditions.Meanwhile, the catalysts can be recycled easily and reused for severaltimes without reducing the yields, which obviously increases theutilization of catalysts.

2. Description of the Related Art

Carbon dioxide is one of the main greenhouse gases, but it is safe,nontoxic, inexpensive, and abundant. Since the industrial revolution,the carbon dioxide level in the atmospheric layer was rising year byyear, enhancing the greenhouse effect, which leads to the globe warmingand the frequent occurrence of the disastrous weather. Therefore, how todispose and use CO₂ has attracted the attention of the whole world.Recently, through the efforts of scientists around the world, it is themain strategy to conceive efficient carbon capture or conversion viachemical technologies. One of the most promising reactions in this areais the cycloaddition reaction of CO₂ and epoxides to cyclic carbonates(CCs). However, numerous reported catalyst systems suffered from harshoperation conditions, and their catalytic activities were limited by therequirement of high pressure and temperature, together with separationdifficulties, which lead to the low efficiency to utilize them. Thus,development of new effective catalytic systems for catalytic conversionwith CO₂ under mild conditions is desired, especially in real worldapplications.

SUMMARY OF THE INVENTION

In order to achieve the desire of the catalytic conversion of carbondioxide under mild conditions, we designed and synthesized the cobalt,chromium, zinc, copper or aluminum-conjugated microporous polymercatalysts (CMP-1, CMP-2, CMP-3, CMP-4 and CMP-5, respectively) based onthe previous research. The chemical conversion of CO₂ with epoxides toform corresponding cyclic carbonates using the CMP-1-5 catalyst systemnot only can obtain ideal effect at mild condition, but also can speedthe production of cyclic carbonate at high temperature and pressure.

Synthesis methods for the cobalt, chromium, zinc, copper oraluminum-conjugated microporous polymer catalysts:

1. Synthesis of Salen:

With Monohydric alcohol (methanol or ethanol) as a solvent, a mixturesolution of R₁-substituted salicylaldehyde and 1,2-diaminocyclohexane(mole ratio=1:1˜30) was stirred for 3˜15 hours at 0˜150° C. to affordthe Salen compounds.

2. Synthesis of Salen-Co-X (Salen-Cr-Cl, Salen-Zn, Salen-Cu):

1) Synthesis of Salen-Co-X:

Synthesis of Salen-Co: To a solution of the Salen in toluene under argonwas added a solution of Co(OAc)₂ in CH₃OH via a syringe, affording adark red reaction mixture. It was heated to 80˜100° C., stirred andrefluxed for 4˜5 hours. Then the reaction mixture was cooled down toroom temperature and concentrated, and the afforded residue wasdissolved in CH₂Cl₂ and filtered through celite. Removing solvent of thefiltrate afforded a dark red powder Salen-Co;

Synthesis of Salen-Co-X: To a solution of the Salen-Co in toluene andCH₂Cl₂ (volume ratio of toluene and CH₂Cl₂=1:3) was added CH₃COOH (HClor HBr or HI) under argon via a syringe. The solution quickly changedfrom red to brown. After stirring at 25° C. for 4˜5 hours, all solventsand excess acid were removed at reduced pressure, affording brown powderSalen-Co-X.

2) Synthesis of Salen-Cr-Cl:

THF was added to a mixture of Salen and CrCl₂ via a syringe under argon.The reaction mixture was stirred at 25° C. for 24 hours. The reactionmixture then was stirred under air at ambient temperature for anadditional 24 hours. After the reaction mixture was poured into diethylether, the organic layer was washed with aqueous saturated NH₄Cl andbrine in turn. After filtration, the organic layer was collectedyielding a brown powder Salen-Cr-Cl.

3) Synthesis of Salen-Zn:

THF was added to a mixture of Salen and Et₂Zn via a syringe under argon.The reaction mixture was stirred at 25° C. for 24 hours. The crudeproduct was isolated from the concentrated reaction mixture by removalof the solvent under reduced pressure. A pure product Salen-Zn wasobtained after recrystallization using THF and water.

4) Synthesis of Salen-Cu:

Anhydrous ethanol was added to a mixture of Salen and Cu(OAc)₂ underargon via a syringe. The reaction mixture was stirred at 80° C. for 24hours. The solvent was removed under reduced pressure, yielding a darkgreen powder Salen-Cu.

3. Synthesis of CMP

1) Synthesis of CMP-1:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Co-X, alkynyl benzeneA (mole ratio of Salen-Co-X and alkynyl benzene A=1:2˜3), copper (I)iodide and tetrakis-(triphenylphosphine)palladium(0) under argon via asyringe. The reaction mixture was heated to 40° C. and stirred for 40min-1 hour. Then, the reaction mixture was heated to 80˜100° C. andrefluxed for 72˜96 hours. The mixture was cooled to room temperature andthe insoluble precipitated polymer was filtered and washed withdichloromethane, methanol, water, and acetone in turn. Furtherpurification of the polymer was carried out by Soxhlet extraction withmethanol and dichloromethane (volume ratio=1:1) for 24˜36 hours. Theproduct CMP-1 was dried in vacuum for 24 hours at 70° C.

2) Synthesis of CMP-2:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Cr-Cl, alkynylbenzene A (mole ratio of Salen-Cr-Cl and alkynyl benzene A=1:2˜3),copper (I) iodide and tetrakis-(triphenylphosphine)palladium(0) via asyringe under argon. The reaction mixture was heated to 40° C. andstirred for 40 min-1 hour. Then, the reaction mixture was heated to80˜100° C. and refluxed for 72˜96 hours. The mixture was cooled to roomtemperature and the insoluble precipitated polymer was filtered andwashed with dichloromethane, methanol, water, and acetone in ruen.Further purification of the polymer was carried out by Soxhletextraction with methanol and dichloromethane (volume ratio=1:1) for24˜36 hours. The product CMP-2 was dried in vacuum for 24 hours at 70°C.

3) Synthesis of CMP-3:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Zn, alkynyl benzene A(mole ratio of Salen-Zn and alkynyl benzene A=1:1˜3), copper (I) iodideand tetrakis-(triphenylphosphine)palladium(0) via a syringe under argon.The reaction mixture was heated to 40° C. and stirred for 40 min-1 hour.Then, the reaction mixture was heated to 80˜100° C. and refluxed for72˜96 hours. The mixture was cooled to room temperature and theinsoluble precipitated polymer was filtered and washed withdichloromethane, methanol, water, and acetone, in turn. Furtherpurification of the polymer was carried out by Soxhlet extraction withmethanol and dichloromethane (volume ratio=1:1) for 24˜36 hours. Theproduct CMP-3 was dried in vacuum for 24 hours at 70° C.

4) Synthesis of CMP-4:

A mixture of toluene and triethylamine (volume ratio of toluene andtriethylamine=3:1) was added to a mixture of salen-Cu, alkynyl benzene A(mole ratio of Salen-Cu and alkynyl benzene A=1:1˜3), copper (I) iodideand tetrakis-(triphenylphosphine)palladium(0) via a syringe under argon.The reaction mixture was heated to 40° C. and stirred for 40 min-1 hourunder an argon atmosphere. Then, the reaction mixture was heated to80˜100° C. and refluxed for 72˜96 hours. The mixture was cooled to roomtemperature and the insoluble precipitated polymer was filtered andwashed with dichloromethane, methanol, water, and acetone in turn.Further purification of the polymer was carried out by Soxhletextraction with methanol and dichloromethane (volume ratio=1:1) for24˜36 hours. The product CMP-4 was dried in vacuum for 24 hours at 70°C.

4. Synthesis of CMP-5: The coordination reaction of the polymer withaluminum was carried out after the polymer was obtained.

1) Synthesis of Salen:

With monohydric alcohol (methanol or ethanol) as a solvent, a mixturesolution of R₁-substituted salicylaldehyde and 1,2-diaminocyclohexane(mole ratio=1:1˜30) was stirred for 1˜15 hours at 0˜150° C. to affordthe Salen compounds;

2) Synthesis of conjugated microporous polymer (CMP):

With tetrakis-(triphenylphosphine)palladium(0) and copper(I) iodide ascatalysts, salen and 1,3,5-triethynylbenzene were mixed with a moleratio of 1:1˜5. The reaction mixture was heated to 20˜150° C. andstirred for 60˜90 hours, yielding the polymer. The mole ratio of thetetrakis-(triphenylphosphine)palladium(0) and 1,3,5-triethynylbenzenewas 1:12˜50, whereas the mole ratio of copper(I) iodide and1,3,5-triethynylbenzene was 1:10˜40.

3) Synthesis of aluminum coordination catalyst (CMP-5):

The aluminum compound was mixed with the CMP obtained got by theprocedure above with a quality ratio of 1:1˜6. Then the mixture reactedat 90˜130° C. for 8˜15 hours, yielding the target CMP-5.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

Before sufficient CO₂ was introduced, the amine compounds were added toa mixture of the CMP-Al and epoxides in which the mole ratio of theCMP-Al and epoxides was 1:1˜25, while the mole ratio of the aminecompounds and the epoxides was 1:5˜1000. Then the reaction was stirredfor 1˜80 hours at 0˜160° C., affording the cyclic carbonates. The aminecompounds mentioned above are quaternary ammonium salts, triethylamineor 4-dimethylamino pyridine.

The structures of the conjugated microporous polymer (CMP) catalysts:

wherein, R₁═—H, -^(t)Bu, -^(i)Bu, —NO₂, —Cl, —CH₂NEt₂, —CH₂N(Bn)Et₂Br,—CH₂N(CH₃)₂CH₂Ph,

X═—OAc or —Cl or —Br or —I or -Et or —OMe or —OEt or—OCH₂CH₂(OCH₂CH)₂Cl. Degree of polymerization for synthesized conjugatedpolymer compound is in the range of 30˜100. These stereochemicalstructures of the polymer catalysts are consisting of three-dimensionalcrosslinking networks. The chemical conversion of CO₂ with terminalepoxides to form corresponding cyclic carbonates under the CMP-1˜5polymer catalyst system above was achieved in excellent yields (35˜90%)of corresponding cyclic carbonate at mild conditions. And the catalystcould be reused without reducing the yields. Simultaneously, holding thereaction condition in the range of 50˜180° C. for the reactiontemperature and 2˜8 MPa for the pressure of CO₂, the yields can be up to90% above while the reaction time only takes 1˜3 hours (excluding theCMP-4).

To prepare CMP-1˜5, the dibromo-functionalized precursor monomersSalen-Co, Salen-Cr-Cl, Salen-Zn, Salen-Cu were first synthesized bycomplexation reaction of metal salt [Co(OAc)₂, CrCl₂, Et₂Zn, Cu(OAc)₂]and Salen. The resulted precursors were polymerized with alkynyl benzene(A) to produce corresponding conjugated microporous polymers (excludingthe CMP-5). The polymers generated by the procedure can adsorb CO₂molecules, increasing the solubility of CO₂ in solvent, which leads tothe improvement of the reaction yields with recycling ability.Simultaneously, the catalysts can obviously shorten the reaction timefor catalyzing the reaction of CO₂ and epoxides at high temperatures andhigh pressures.

Synthetic routes for the polymers (CMP-1,CMP-2,CMP-3,CMP-4):

Synthetic routes for CMP-5:

The coupling of epoxides and CO₂ by polymer catalyst (CMP):

CMP: CMP-1, CMP-2, CMP-3, CMP-4 or CMP-5; Co-catalyst: quaternaryammonium salts (Tetrabutyl ammonium bromide and tetrabutyl ammoniumchloride and tetrabutyl ammonium acetate), TEA, DMAP; R₂═—Me, —C₂H₅,-Ph, —CH₂Ph, -Bu or —C₈H₁₇. The amount of substance ratio for epoxides,CMP and Co-catalyst is about 200˜2000:1:1.

In this invention, a series of new metal-conjugated microporous polymercatalysts were synthesized and used to catalyze the reaction of epoxidesand CO₂ to produce corresponding cyclic carbonates at ambient pressuresand temperatures. The procedure is a breakthrough for overcoming thelimitation of this reaction which can only occur at high pressure of CO₂and temperature catalyzed by other catalysts. The yields of cycliccarbonates were in the range of 30˜90% at ambient pressures andtemperatures. Remarkably, the polymer catalyst can be reused for manytimes without reducing the yields. Besides, elevating the pressure andthe temperature can shorten the reaction time to 1˜6 hours, with theyields above 90%.

The various features of novelty which characterize the invention arepointed out with particularity in the claims annexed to and forming apart of the disclosure. For a better understanding of the invention, itsoperating advantages, and specific objects attained by its use,reference should be had to the drawing and descriptive matter in whichthere are illustrated and described preferred embodiments of theinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

Description of the figures is provided below:

FIG. 1: ¹H NMR of the Salen[N,N-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane as anexample] (CDCl₃, measured under 400 MHz NMR equipment);

FIG. 2: ¹H NMR of the 4-Methyl-[1,3]dioxolan-2-one (CDCl₃, measuredunder 400 MHz NMR equipment);

FIG. 3: ¹³C NMR of the 4-Methyl-[1,3]dioxolan-2-one (CDCl₃, measuredunder 400 MHz NMR equipment);

FIG. 4: ¹H NMR of the 4-Choloro-[1,3]dioxolan-2-one (measured underCDCl₃, 400 MHz NMR equipment);

FIG. 5: ¹³C NMR of the 4-Choloro-[1,3]dioxolan-2-one (CDCl₃, measuredunder 400 MHz NMR equipment);

FIG. 6: ¹H NMR of the 4-Ethyl-[1,3]dioxolan-2-one (CDCl₃, measured under400 MHz NMR equipment);

FIG. 7: ¹³C NMR of the 4-Ethyl-[1,3]dioxolan-2-one (CDCl₃, measuredunder 400 MHz NMR equipment);

FIG. 8: ¹H NMR of the 4-Butyl-[1,3]dioxolan-2-one (CDCl₃, measured under400 MHz NMR equipment);

FIG. 9: ¹³C NMR of the 4-Butyl-[1,3]dioxolan-2-one (CDCl₃, measuredunder 400 MHz NMR equipment);

FIG. 10. ¹H NMR of the 4-Phenyl-[1,3]dioxolan-2-one (CDCl₃, measuredunder 400 MHz NMR equipment);

FIG. 11: ¹³C NMR of the 4-Phenyl-[1,3]dioxolan-2-one (CDCl₃, measuredunder 400 MHz NMR equipment);

FIG. 12: The FT-IR spectra of CMP-1-1;

FIG. 13: The FT-IR spectra of CMP-1-2;

FIG. 14: The FT-IR spectra of CMP-2-1;

FIG. 15: The FT-IR spectra of CMP-3-1;

FIG. 16: Solid-state NMR spectra for the CMP-5-1;

FIG. 17: Solid-state NMR spectra for the CMP-1-1;

FIG. 18: Solid-state NMR spectra for the CMP-1-2;

FIG. 19: Solid-state NMR spectra for the CMP-2-1;

FIG. 20: Solid-state NMR spectra for the CMP-3-1;

FIG. 21: Solid-state NMR spectra for the CMP-4-1.

DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

The invention is not limited by the embodiments described above whichare presented as examples only but can be modified in various wayswithin the scope of protection defined by the appended patent claims.

The technological invention embodiment is not limited in the specificexamples below, including the any combination of these detailedimplementation programs.

EXAMPLE 1

1. Synthesis of Salen-Co: A solution of Co(OAc)₂ (1 mmol) in CH₃OH (10ml) was added to a solution of the Salen (0.75 mmol) in 10 mL anhydroustoluene (10 ml) via a syringe. The reaction mixture was refluxed for 5hours at 80° C., yielding the target Salen-Co;

2. Synthesis of Salen-Co-OAc: The acetic acid (6.5 mmol) was added to asolution of the Salen-Co (0.65 mmol) in toluene (6 ml) and CH₂Cl₂ (18ml) via a syringe under argon. The mixture was stirred for 5 hours at25° C., yielding the target Salen-Co-OAc, and its NMR spectrum was shownin FIG. 2.

3. Synthesis of CMP-1-1: Salen-Co-OAc (0.45 mmol),1,3,5-triethynylbenzene (1.35 mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in amixture of toluene (15 ml) and triethylamine (5 ml). Then the reactionmixture was refluxed at 85° C. for 72 hours. After post-processing,CMP-1-1 was obtained. The FT-IR spectra and the Solid-state NMR spectraof the CMP-1-1 were shown in FIG. 12 and FIG. 17, respectively.

4. Catalyzing for the coupling reaction of CO₂ and epoxides:

1) A mixture of 100 mg CMP-1-1, 600 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours at ambient pressure and temperature, and theyield of the propylene carbonate is 87.5%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 6 hours at 45° C., and theyield of the propylene carbonate is 94.5%. The ¹H and ¹³C NMR for thepropylene carbonate were shown in FIG. 3 and FIG. 4.

EXAMPLE 2

1. Synthesis of Salen-Co: A solution of Co(OAc)₂ (1 mmol) in CH₃OH (10ml) was added to a solution of the Salen (0.6 mmol) anhydrous toluene(10 ml) via a syringe. Then the reaction mixture was refluxed for 5hours at 80° C., yielding the target Salen-Co;

2. Synthesis of Salen-Co-OAc: The acetic acid (5 mmol) was added to asolution of the Salen-Co (0.5 mmol) in toluene (5 ml) and CH₂Cl₂ (15 ml)via a syringe under argon. Then the mixture was stirred for 5 hours at25° C., yielding the target Salen-Co-OAc, and the NMR spectrum was shownin FIG. 2.

3. Synthesis of CMP-1-1: Salen-Co-OAc (0.6 mmol),1,3,5-triethynylbenzene (2.4 mmol), copper(I) iodide (60 mg) andtetrakis-(triphenylphosphine)palladium(0) (100 mg) were dissolved in amixture of toluene (16 ml) and triethylamine (6 ml). Then the reactionmixture was refluxed at 85° C. for 72 hours. After post-processing,CMP-1-1 was obtained. The FT-IR spectra and the Solid-state NMR spectraof the CMP-1-1 were shown in FIG. 12 and FIG. 17, respectively.

4. Catalyzing the coupling reaction of CO₂ and epoxides:

1) A mixture of 100 mg CMP-1-1, 400 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours at ambient pressure and temperature, and theyield of the propylene carbonate is 80.5%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 4 hours at 60° C., and theyield of the propylene carbonate is 98.5%. The ¹H and ¹³C NMR for thepropylene carbonate were shown in FIG. 3 and FIG. 4;

3) A mixture of 100 mg CMP-1-1, 200 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at the ambient pressure and temperature,and the yield of the propylene carbonate is 56.5%;

4) With 5.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 12 hours at 30° C., and theyield of the propylene carbonate is 94.0%. The ¹H and ¹³C NMR for thepropylene carbonate were shown in FIG. 3 and FIG. 4.

EXAMPLE 3

1. Synthesis of Salen-Co: A solution of Co(OAc)₂ (1 mmol) in CH₃OH (8ml) was added to a solution of the Salen (0.5 mmol) in 8 mL anhydroustoluene (10 ml) via a syringe. The reaction mixture was refluxed for 5hours at 80° C., yielding the target Salen-Co;

2. Synthesis of Salen-Co-OAc: The acetic acid (9 mmol) was added to asolution of Salen-Co (0.65 mmol) in toluene (5 ml) and CH₂Cl₂ (15 ml)via a syringe under argon. The mixture was stirred for 6 hours at 25°C., yielding the target Salen-Co-OAc, and the NMR spectrum was shown inFIG. 2.

3. Synthesis of CMP-1-1: Salen-Co-OAc (0.6 mmol),1,3,5-triethynylbenzene (2.0 mmol), copper(I) iodide (50 mg) andtetrakis-(triphenylphosphine)palladium(0) (100 mg) were dissolved in amixture of toluene (16 ml) and triethylamine (5 ml). Then the reactionmixture was refluxed at 85° C. for 72 hours. After post-processing,CMP-1-1 was obtained. The FT-IR spectra and the Solid-state NMR spectraof the CMP-1-1 were shown in FIG. 12 and FIG. 17 respectively.

4. Catalyzing the coupling reaction of CO₂ and epoxides:

-   1) A mixture of 100 mg CMP-1, 400 mg TBAB and 1.75 ml propylene    oxide was stirred for 48 hours in CO₂ at ambient pressure and    temperature, and the yield of the propylene carbonate is 96.5%;-   2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1, 600 mg    TBAB and 1.75 ml propylene oxide was stirred for 3 hours at 70° C.,    and the yield of the propylene carbonate is 97%;-   3) A mixture of 100 mg CMP-1, 200 mg TBAB and 1.75 ml propylene    oxide was stirred for 48 hours in CO₂ at the ambient pressure and    temperature, and the yield of the propylene carbonate is 66.5%;-   4) With 5.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1, 600 mg    TBAB and 1.75 ml propylene oxide was stirred for 12 hours at 30° C.,    and the yield of the propylene carbonate is 94.0%;-   5) A mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene    oxide was stirred for 60 hours in CO₂ at ambient pressure and    temperature, and the yield of the propylene carbonate is 91.5%;-   6) A mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene    oxide was stirred for 36 hours in CO₂ at ambient pressure and    temperature, and the yield of the propylene carbonate is 76.5%.

EXAMPLE 4

1. Synthesis of Salen-Co: A solution of Co(OAc)₂ (1 mmol) in CH₃OH (10ml) was added to a solution of the Salen (0.6 mmol) in 10 ml anhydroustoluene via a syringe. The reaction mixture was refluxed for 5 hours at80° C., yielding the target Salen-Co.

2. Synthesis of Salen-Co-OAc: The acetic acid (5 mmol) was added to asolution of the Salen-Co (0.5 mmol) in toluene (5 ml) and CH₂Cl₂ (15 ml)via a syringe under argon. The mixture was stirred for 5 hours at 25°C., yielding the target Salen-Co-OAc, and the NMR spectrum was shown inFIG. 2.

3. Synthesis of CMP-1-2: Salen-Co-OAc (0.6 mmol), 1,4-diacetylenebenzene(1.2 mmol), copper(I) iodide (50 mg) andtetrakis-(triphenylphosphine)palladium(0) (90 mg) were dissolved in amixture of toluene (16 ml) and triethylamine (6 ml). Then the reactionmixture was refluxed at 85° C. for 72 hours. After post-processing,CMP-1-2 was obtained. The FT-IR spectra and the Solid-state NMR spectraof the CMP-1-2 were shown in FIG. 13 and FIG. 18, respectively.

4. Catalyzing for the coupling reaction of CO₂ and epoxides:

1) A mixture of 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 66.5%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 90° C., and theyield of the propylene carbonate is 85.9%;

3) With 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxide in themixture, the reaction mixture was stirred for 24 hours in CO₂ at ambientpressure and temperature, and the yield of the propylene carbonate is52.5%;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 110° C., and theyield of the propylene carbonate is 91.1%;

5) With 4.0 MPa CO₂ introduced, a mixture of 100 mg CMP-1-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 1 hour at 120° C., and theyield of the propylene carbonate is 64.2%. The ¹H and ¹³C NMR spectrumsfor the propylene carbonate were shown in FIG. 3 and FIG. 4.

EXAMPLE 5

1. Synthesis of Salen-Cr-Cl: The chromium (II) chloride (0.8 mmol) andSalen(N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane (0.6mmol) were dissolved in dried THF (12 mL). The mixture was stirred underargon at 25 oC for 24 hours and for another 24 hours in the air. Afterthat the compound Salen-Cr-Cl was obtained.

2. Synthesis of CMP-2:

1) Synthesis of CMP-2-1: Salen-Cr-Cl (0.4 mmol), 1,3,5-triethynylbenzene(1.2 mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in amixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-2-1. The FT-IR spectra and the Solid-state NMR spectra ofthe CMP-2-1 were shown in FIG. 14 and FIG. 19, respectively;

2) Synthesis of CMP-2-2: Salen-Cr-Cl (0.45 mmol), 1,4-diethynylbenzene(1.35 mmol), copper(I) iodide (30 mg) andtetrakis-(triphenylphosphine)palladium(0) (60 mg) were dissolved in amixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-2-2;

3) Synthesis of CMP-2-3: Salen-Cr-Cl (0.4 mmol),tetrakis(4-ethynylphenyl)methane (1.2 mmol), copper(I) iodide (40 mg)and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved ina mixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-2-3.

3. Catalyzing for the coupling reaction of CO₂ and epoxides:

1) A mixture of 100 mg CMP-2-1, 500 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 67.7%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 1 hour at 100° C., and theyield of the propylene carbonate is 98.5%. The NMR spectrums for theproduct were shown in FIG. 2 and FIG. 3;

3) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 1.96 ml epichlorohydrin was stirred for 1 hour at 100° C., and theyield of the corresponding cyclic carbonate is 99.1%. The NMR spectrumsfor the product were shown in FIG. 4 and FIG. 5;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 2.146 ml 1,2-epoxybutane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.0%. The NMR spectrumsfor the product were shown in FIG. 6 and FIG. 7;

5) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 3.01 ml 1,2-epoxyhexane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.7%. The NMR spectrumsfor the product were shown in FIG. 8 and FIG. 9;

6) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-1, 600 mg TBABand 2.85 ml styrene oxide was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.3%. The NMR spectrumsfor the product were shown in FIG. 10 and FIG. 11;

7) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-2-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 86.5%.

EXAMPLE 6

1. Synthesis of Salen-Zn: The Et₂Zn (0.4 ml, 1.0 M in hexane) and Salen(N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane (0.4mmol) and were dissolved in dried THF (20 ml). The mixture was stirredunder argon at 25° C. for 24 hours. After that the compound Salen-Zn wasobtained.

2. Synthesis of CMP-3:

1) Synthesis of CMP-3-1: Salen-Zn (0.35 mmol), 1,3,5-triethynylbenzene(1.05 mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in amixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-3-1. The FT-IR spectra and the Solid-state NMR spectra ofthe CMP-3-1 were shown in FIG. 15 and FIG. 20, respectively.

2) Synthesis of CMP-3-2: Salen-Zn (0.4 mmol), 1,4-diethynylbenzene (1.2mmol), copper(I) iodide (35 mg) andtetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in amixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-3-2.

3) Synthesis of CMP-3-3: Salen-Zn (0.4 mmol),tetrakis(4-ethynylphenyl)methane (1.2 mmol), copper(I) iodide (40 mg)and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved ina mixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-3-3.

3. Catalyzing the coupling reaction of CO₂ and epoxides:

1) A mixture of 100 mg CMP-3-1, 500 mg TBAB and 1.75 ml propylene oxidewas stirred 48 hours in CO₂ at ambient pressure and temperature, and theyield of the propylene carbonate is 85.1%;

2) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and theyield of the propylene carbonate is 95.2%;

3) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 1.96 ml epichlorohydrin was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 99.6%;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600mg TBABand 2.146 ml 1,2-epoxybutane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.5%;

5) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 3.01 ml 1,2-epoxyhexane was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 98.3%;

6) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-1, 600 mg TBABand 2.85 ml styrene oxide was stirred for 2 hours at 100° C., and theyield of the corresponding cyclic carbonate is 96.6%;

7) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-3-2, 600 mg TBABand 1.75 ml propylene oxide was stirred for 1 hour at 100° C., and theyield of the corresponding cyclic carbonate is 88.7%.

EXAMPLE 7

1. Synthesis of Salen-Cu: The Cu(OAc)₂ (0.5 mmol) and Salen(N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane, 0.5mmol) and were dissolved in dried ethanol (20 mL). The mixture wasstirred at 80° C. for 24 hours. After that the compound Salen-Cu wasobtained.

2. Synthesis of CMP-4:

1) Synthesis of CMP-4-1: Salen-Cu (0.46 mmol), 1,3,5-triethynylbenzene(1.32 mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in amixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-4-1. The Solid-state NMR spectra of the CMP-4-1 were shownin FIG. 21.

2) Synthesis of CMP-4-2: Salen-Cu (0.4 mmol), 1,4-diethynylbenzene (1.2mmol), copper(I) iodide (40 mg) andtetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in amixture of toluene (12 ml) and triethylamine (4 ml). The reactionmixture was refluxed at 80° C. for 72 hours, yielding the neededcompound CMP-4-2.

3) Synthesis of CMP-4-3: Salen-Cu (0.45 mmol),tetrakis(4-ethynylphenyl)methane (1.35 mmol), copper(I) iodide (40 mg)and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved ina mixture of toluene (15 ml) and triethylamine (5 ml). The reactionmixture was refluxed at 85° C. for 72 hours, yielding the neededcompound CMP-4-3.

3. Catalyzing for the coupling reaction of CO₂ and epoxides:

1) A mixture of 100 mg CMP-4-1, 400 mg TBAB and 1.75 ml propylene oxidewas stirred for 72 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 58.5%;

2) A mixture of 100 mg CMP-4-1, 500 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 51.3%;

3) A mixture of 100 mg CMP-4-1, 200 mg TBAB and 1.75 ml propylene oxidewas stirred for 48 hours in CO₂ at ambient pressure and temperature, andthe yield of the propylene carbonate is 42.7%;

4) With 3.0 MPa CO₂ introduced, a mixture of 100 mg CMP-4-1, 600 mg TBABand 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and theyield of the propylene carbonate is 52.7%.

EXAMPLE 8

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofsalicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) wasstirred at 40° C. for 5 hours, yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlEt₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 2 hours, the yield of the propylene carbonateis 30%.

EXAMPLE 9

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofsalicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) wasstirred at 40° C. for 5 hours, yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlCl₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-Al.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 5 hours, the yield of the propylene carbonateis 39.8%.

EXAMPLE 10

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with propanol as solvent, a mixture of^(t)Bu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 50° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlBr₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-Al.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 10 hours, the yield of the propylene carbonateis 52.1%.

EXAMPLE 11

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofCl-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 25° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlEt₃ (20 mg) was stirred and refluxedat 140° C. for 8 hours, yielding the target catalyst CMP-5-1;

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 20 hours, the yield of the propylene carbonateis 63.4%.

EXAMPLE 12

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofCl-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 25° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and AlCl₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1;

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 10° C. for 6 hours, the yield of the propylene carbonateis 40.3%.

EXAMPLE 13

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with methanol as solvent, a mixture ofNO₂-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 50° C. for 10 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (100 mg) and AlEt₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst CMP-5-1;

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 5 hours, the yield of the propylene carbonateis 53.5%.

EXAMPLE 14

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with i-propanol as solvent, a mixture of^(i)Bu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 70° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (100 mg) and AlBr₃ (20 mg) was stirred and refluxedat 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 10 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 15° C. for 20 hours, the yield of the propylene carbonateis 83.7%.

EXAMPLE 15

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with i-propanol as solvent, a mixture of^(i)Bu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane(7.0 mmol) was stirred at 70° C. for 5 hours, yielding the Salencompound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and Al(OEt)₃ (20 mg) was stirred andrefluxed at 90° C. for 8 hours, yielding the target catalyst CMP-5-1.

4) Catalyzation for the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 30 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:10)was stirred at 0° C. for 5 hours, the yield of the propylene carbonateis 68.2%.

EXAMPLE 16

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with hexanol as solvent, a mixture ofCH₂N(CH₃)₂CH₂Ph-substituted salicylaldehyde (6.0 mmol) and1,2-diaminocyclohexane (7.0 mmol) was stirred at 80° C. for 5 hours,yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and Al(OMe)₃ (20 mg) was stirred andrefluxed at 90° C. for 8 hours, yielding the target catalyst compoundCMP-Al.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 30 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5)was stirred at 0° C. for 13 hours, the yield of the propylene carbonateis 89.6%.

EXAMPLE 17

Synthesis of CMP-5-1 and its catalyzation for the coupling reaction ofCO₂ and epoxides:

1) Synthesis of Salen: with butanol as solvent, a mixture ofCH₂N(Bn)Et₂Br-substituted salicylaldehyde (6.0 mmol) and1,2-diaminocyclohexane (7.0 mmol) was stirred at 25° C. for 5 hours,yielding the Salen compound;

2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol),copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0)(10 mg) was stirred at 30° C. for 60 hours, yielding the target polymerCMP;

3) A mixture of CMP (20 mg) and Al(OMe)₃ (20 mg) was stirred andrefluxed at 100° C. for 10 hours, yielding the target catalyst CMP-5-1.

4) Catalyzing the coupling reaction of CO₂ and epoxides:

With sufficient CO₂ introduced, a mixture of 10 mg CMP-5-1 and 30 mgpropylene oxide (mole ratio of ammonium salt and propylene oxide=1:5),was stirred at 0° C. for 20 hours, the yield of the propylene carbonateis 93.5%.

Using the polymers as catalysts to catalyze the coupling reaction of CO2and epoxides, the yields of the cyclic carbonates were in the range of35˜90%. The catalysts can be reused for several times without reducingthe yields which can reach to 90% above at high pressure (2˜8 MPa) andthe temperature of 50˜120 oC for 1˜3 hours. The procedure is abreakthrough for overcoming the limitation of this reaction which canonly occur at high pressure and temperature catalyzed by othercatalysts. Meanwhile the reuse of the catalysts can figure out thetroubles caused by the low efficiency of the other catalysts.

What is claimed is:
 1. A metal-conjugated microporous polymer having thefollowing structure:

wherein, R₁═—H, -^(t)Bu, -^(i)Bu, —NO₂, —Cl, —CH₂NEt₂, —CH₂N(Bn)Et₂Br,—CH₂N(CH₃)₂CH₂Ph,

M is Co, Cr, Zn, Cu, or Al; X═—OAc or —Cl or —Br or —I or -Et or —OMe or—OEt or —OCH₂CH₂(OCH₂CH)₂Cl, n represents degree of polymerization ofthe metal-conjugated microporous polymer and is in the range of 30˜100;when M is Co, R₂ is not


2. The metal-conjugated microporous polymer polymer of claim 1 wherein Mis Cr.
 3. The metal-conjugated microporous polymer polymer of claim 1wherein R₂ is


4. The metal-conjugated microporous polymer polymer of claim 1 wherein Mis Co.
 5. A method for preparing the metal-conjugated microporouspolymer polymer of claim 1 wherein M is Co, Cr, Zn, or Cu, and themethod comprises: synthesis of the metal-conjugated microporous polymer:with anhydrous toluene and TEA as solvent (volume ratio=3˜4:1), CuI andtetrakis-(triphenylphosphine)palladium(0) as catalyst, a mixturesolution of alkynyl benzene A and Salen-M-X or Salen-M (moleratio=1˜4:1) is stirred under argon for 60˜90 hours at 25˜100° C.,affording the metal-conjugated microporous polymer, wherein the moleratio of CuI and alkynyl benzene A is 1:5˜10 and, and the mole ratio oftetrakis-(triphenylphosphine)palladium(0) and alkynyl benzene A is1:20˜30 .
 6. A method for preparing the metal-conjugated microporouspolymer of claim 1, wherein M is Al, and the method comprises: 1)synthesis of a conjugated microporous polymer (CMP): with anhydroustoluene and TEA as solvent (volume ratio=3˜4:1),tetrakis-(triphenylphosphine)palladium(0) and CuI as catalyst, a mixturesolution of alkynyl benzene A and Salen (mole ratio=1:1˜5) is stirredunder argon for 60˜90 hours at 20˜150° C., affording the CMP, wherein,the mole ratio of CuI and alkynyl benzene A is 1:10˜40, and the moleratio of or tetrakis-(triphenylphosphine)palladium(0) and alkynylbenzene A is 1:12˜50; 2) synthesis of the metal -conjugated microporouspolymer: with anhydrous toluene as a solvent, a mixture solution of analuminum compound and CMP (mass ratio=1:1˜6) is stirred for 8˜15 hoursat 90˜130° C., affording the metal aluminum-conjugated microporouspolymer polymer, wherein, the aluminum compound is AlCl₃, AlBr₃, AlEt₃,Al(OMe)₃, Al(OMe)₃, or Al(OCH₂CH₂(OCH₂CH)₂Cl)₃.
 7. The method of claim 5wherein: the amount of anhydrous toluene required by each 1 mmolSalen-M-X , or Salen-M is 30˜50 ml.
 8. The method of claim 6 wherein:the mole ratio of alkynyl benzene A and Salen in step 1) is 1:1˜3; themole ratio of tetrakis-(triphenylphosphine)palladium(0) or CuI and1,3,5-triethynylbenzene in step 1) is 1:12˜28, and 1:10˜25 respectively;the mass ratio of aluminum compound and CMP in step 2) is 1:1˜2.5. 9.The method of claim 6 wherein: the amount of anhydrous toluene requiredby each 1 mmol Salen in step 1) is 20˜25 ml; and the amount of anhydroustoluene required by each 1 g CMP in step 2) is 15˜20 ml.
 10. The methodof claim 5, wherein: the alkynyl benzene A is 1,3,5-triethynylbenzene,1,4-diethynylbenzene or tetrakis(4-ethynylphenyl)methane.
 11. The methodof claim 6, wherein: the alkynyl benzene A is 1,3,5-triethynylbenzene,1,4-diethynylbenzene or tetrakis(4-ethynylphenyl)methane.
 12. A methodof making a cyclic carbonate comprising coupling CO₂ and an epoxide inthe presence of the metal-conjugated microporous polymer of claim 1 as acatalyst at 0˜180° C. and 0.1˜8.0 MPa CO₂ pressure.
 13. The method ofclaim 12, wherein: general procedure for the catalytic reaction of CO₂and epoxides at ambient pressure and temperature: in the presence of anamine compound, a mixture solution of the metal-conjugated microporouspolymer, and the epoxide (mass ratio=1:10˜50) is stirred for 12˜72 hoursat ambient pressure and temperature, affording the corresponding cycliccarbonate, wherein, the mole ratio of the amine compound and epoxide is1:10˜100, and M is not Al.
 14. The method of claim 12, wherein: generalprocedure for the catalytic reaction of CO₂ and epoxide at a wide rangeof temperature and pressure: in the presence of a amine compound, amixture solution of the metal-conjugated microporous polymer polymer andthe epoxide (mass ratio=1:10˜50) is stirred for 1˜6 hours at 50˜160° C.and 2˜8 MPa CO₂ pressure, affording the corresponding cyclic carbonate,wherein, the mole ratio of the amine compound and epoxide is 1:10˜100,and M is not Al.
 15. The method of claim 12, wherein: M is Al, generalprocedure to catalyze reaction of CO₂ and the epoxide: in the presenceof an amine compound, a mixture solution of the metal-conjugatedmicroporous polymer and epoxide (mass ratio =1:1˜25) is stirred for 3˜80hours at 0˜160° C., affording the corresponding cyclic carbonate,wherein, the mole ratio of the amine compound and epoxide is 1:5˜1000.16. The method of claim 15, wherein, the mole ratio of the aminecompound and epoxide is 1:900.
 17. The method of of claim 12, whereinthe reaction is conducted in the presence of an amine compound selectedfrom the group consisting of quaternary ammonium salts, triethylamine(TEA), dimethylaminopyridine (DMAP), and mixtures thereof.
 18. Themethod of claim 12, wherein the epoxide is selected from the groupconsisting of propylene oxide, epichlorohydrin, 2-ethyloxirane,2-butyloxirane, 2-phenyloxirane, and mixtures thereof.